Ruthenium(0) Catalyzed Endiyne−α-Ketol [4 + 2] Cycloaddition: Convergent Assembly of Type II Polyketide Substructures via C–C Bond Forming Transfer Hydrogenation

Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to α-ketols (α-hydroxyketones) in the presence of Ru(0) catalysts derived from Ru3(CO)12 and RuPhos or CyJohnPhos, successive redox-triggered C–C coupling occurs to generate products of [4 + 2] cycloaddition. The proposed catalytic mecha...

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Bibliographic Details
Published in:	Journal of the American Chemical Society Vol. 137; no. 18; pp. 5883 - 5886
Main Authors:	Saxena, Aakarsh, Perez, Felix, Krische, Michael J
Format:	Journal Article
Language:	English
Published:	United States American Chemical Society 13-05-2015
Subjects:	Alkynes - chemistry Catalysis Cyclization Hydrogenation Ketones - chemistry Molecular Structure Organometallic Compounds - chemistry Polyketides - chemical synthesis Polyketides - chemistry Ruthenium - chemistry
Online Access:	Get full text
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Summary:	Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to α-ketols (α-hydroxyketones) in the presence of Ru(0) catalysts derived from Ru3(CO)12 and RuPhos or CyJohnPhos, successive redox-triggered C–C coupling occurs to generate products of [4 + 2] cycloaddition. The proposed catalytic mechanism involves consecutive alkyne-carbonyl oxidative couplings to form transient oxaruthanacycles that suffer α-ketol mediated transfer hydrogenolysis. This process provides a new, convergent means of assembling Type II polyketide substructures.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	0002-7863 1520-5126
DOI:	10.1021/jacs.5b02755